Destructive hydrogenation of distillable carbonaceous materials



Aug. 1, 1933. M, PlER AL 1,920,888

DESTRUCTIVE HYDROGENATION OF DI STILLABLE- CARBONACEOUS MATERIALS Filed Oct. 1,1929 2 Sheets-Sheet 1 Naflrias Pier W/lhe/m fiumpf I NVENTORS ATTORNEY Aug. 1, 1933. M. PIER El AL DESTRUCTIVE HYDROGENATION OF DISTILLABLE CARBQNACEOUS MATERIALS pllll" 2 Sheets-Sheet 2 Filed Oct. 1. 1929 INVENTORS Patented Aug. 1, 1933 Q i Y UNITED STATES PATENT OFFICE DESTRUCTIVE HYDROGENATION OF DIS- TILLABLE CARBONACEOUS MATERIALS Mathias. Pier, Heidelberg, and Wilhelm Rumpf,

Ludwigshafen-on-the-R,hine, Germany, assignors, by mesne assignments, to Standard- I. G. Company, Linden, N. J., a Corporation of Delaware Application October 1, 1929, Serial No. 396,486,

and in Germany October 9, 1928 2 Claims. (01. 196-116) This invention relates to improvements in or the formation of injurious coke crusts can the destructive hydrogenation of distillable caralso be prevented by immediately removing the bonaceous materials. coke which is formed at some place or the other When in the destructive hydrogenation of disby means of special apparatus. Care should be 5 tillable carbonaceaus materials and in partictaken that no rough places are present on the 0 ular of carbonaceous materials inthe liquid inner walls of the tubes or vessels to which coke form, 'such as coal sludges, tars, mineral oils, may attach itself or at which exothermic chemiextraction, distillation and conversion products cal side reactions may occur. thereof andthe like with hydrogen or gases con- Another method of working in order to pre-' 10 taining or supplying hydrogen, the reaction vesvent local superheating' is by not allowing the 65 sel is heated from the outside, it is found that heating gases, which inthis-case may be at a although generally speaking no attack of the temperature above 800 centigrade, to come into metal walls by hydrogen occurs in the presence direct. contact with the walls of the tubes or of oil, it sometimes nevertheless happens that vessel but to arrange a protecting tube between tubes crack and are attacked bythe hydrogen. the same. In the intermediate space between 70 The probable reason for this is that in consetwo tubes the heat is distributed uniformly and quence of local superheating or in consequence is then also transferred uniformly to the tubes. ofsome other cause, a certain amount of a coke It is of particular advantage in some cases to crust has been deposited in some part of the work with vertical tubes because then the oil apparatus and this hinders the transference of is uniformly distributed over the inner surfaces 75 heat from the metal walls to the materials under of the said walls. treatment, for example coal sludge or oil. Con- By the process in accordance with the present sequently a strong heating of the wall at these invention it is possible to employ comparatively places occurs'even when the hot gases are not at less resistant material for the walls of the ap too high a. temperature. At these places crackparatus, for example weakly alloyed steel. "It 80 ing of the tubes occurs, probably assisted or is also advantageous to provide the parts which caused by an attack of hydrogen on the crude are heated to a relatively high temperature with materials. It has already been proposed to emspecial jackets of resistant material, whilst the ploy heating media .which have a temperature other parts may be constructed of less expensive which is notappreciably higher than the reacmaterial.

tion temperature. This, however, leads to in- The process according to the present invenconveniences in heat technique, since in this case tion may be carried out under any of the condiheating surfaces having a very considerable area tions of temperature and pressure suitable for are q r d destructive hydrogenation for example at ele- We have now found that heating media which vated-pressure', and catalysts in particular those have a temperature substantially higher, at least immune from poisoning by sulphur, may be emcentrigrade higher, than the reaction tem- .ployed if desired, and in particular catalysts peraturecan be employed, provided that they comprising cobalt or a metal from the sixth do not have a temperature above 800 centigrade, group of the periodic system, such'as molybdewhen provision is made ,for a uniform flow ofv num, tungsten or chromium as such or in the 95 heat from the heating medium to the materials form ofv its compounds. under treatment of the materials to be treat- The temperatures of the'reaction materials in ed. In this manner the materials may betprethe said destructive hydrogenation process will heated prior to being subjected to destructive usually range between about 300 and 600 C.

hydrogenation or may be heated during the and may in some cases attain 700 C., but prefdestructive hydrogenation. The said materials erably temperatures of between about 380 and are hereinafter referred to for the sake of brevity 550 C. are employed. p as the charge. For example, in order to prevent The pressure employed will usually exceed 50 asurpassing of the maximum temperature'hereatmosphe ic. Thus fo e a p pressures Of inbeforementioned, the efiluent heating gases, 20 or more atmospheres may be employed, and

which have already been cooled to a certain exp e a y h er p s Such example tent, may be mixed with a quantity of, flame as 50, 100, 200,300, 500, "600, 1000, 2000, 3000,

gases suflicient to heat them up to the desired 5000-or'even more atmospheres are made'use of temperature and recycled. The superheating in the process.

angles to each other, and Figures 3 and 4 being a vertical section and a plan of a further modification of the apparatus having vertical pipes,

' which drawings illustrate arrangements of apparatus according to this invention, by way of example, but the invention is not restricted thereto. In Figures 1 and 2 o is a chamber and a are burners for the combustion of gases therein. b is a passage in thewall of the said chamber and c are openings for the admission of recycled gases from the said passage into the chamber 0 wherein the latter gases are mixed with the said gases of combustion. e is a larger chamber containing a system .of coils p and separated from the chamber 0 by the baflle plate 6 around which the mixture of gases from the chamberopassesintothechambere. fisa pipe for the introduction into the coil system p of the materialsto be subjected to destructive hydrogenation. q is a pipe for the removal of the said materials from the tube system. h is an, opening for the removal of the heating gases from the chamber by way of the flue w. i is a,

gas pump for maintaining the gases issuing at h in circulation. m is a pipe for recirculating the heating gases and n is a branch pipe controlled by the valve In for the removal of gases from the cycle.

Referring first to Figures 1 and 2 of the accompanying drawings, flame gases coming from a burner a are mixed at b with circulating heating gases, which have already been employed for heating, in order to reduce the temperature of the said flame gases; they then pass through numerous openings c, pass round a bame plate d and finally enter into a closed chamber e in which are arranged the conduit pipes p for the reaction materials. Tar and hydrogen, for example, enter the coil of pipes at f at room temperature and under a pressure of 200 atmospheres, and leave the same at g with a temperature of about 450 C. The upper windings of the pipes have a special insulation, which is indlcated by dotted lines, to protect them from superheating. -The heating gases leave the heating chamber e at h, and are circulated by a gas pump i. They then pass either into the flue through the valve k, or back into the chamher at b.

w A mixture of tar and hydrogen isintroduced under a pressure of about 200 atmospheres and at room temperature through the pipe I into the coil p and is heated therein to a'temperature of about 450 C. at which temperature it is drawnoffatgandpassedintoahighpressure reaction vessel not shown in the drawings and containing a catalyst prepared from tungstic acid and magnesia. About 90 per cent of .the tar is in this way converted into low boiling hydrocarbons of gasoline character. No deposition of coke takes place in or on the preheating coil owing to the fact that the temperature .of the flame gases has been reduced to about 850' C. and that a very uniform heating of the mixher e containing the coil p, through which a charge of materials which is to be subjected to destructive hydrogenation is passed. The heating gases issue from the said chamber e through the-opening h and are passed on to the circulating gas pump 1, from which the said gases may either be withdrawn through the pipe line i 1: controlled by the valve k, or the said gases may be recycled through the pipe line m. The materials which are to be heated and to be subjected to destructive hydrogenation are introduced to the coil 12 by way of the pipe 1 and removed by the pipe g. A mixture of crude oil and hydrogen is introduced under a' pressure of 200 atmospheres and at room temperature by way of the pipe f to the coil :1, wherein the said mixture is preheated to a temperature of 450 C., with which it leaves the said chamber at g. The heating gases have a temperature of-about 800 0. and the gases leaving the chamber at h, which have been employed for 1 heating, have a temperature of about 380 C. The preheatedmixture of crudeoil and hydrogenating gas is passed directly from g into a reaction vessel containing a catalyst prepared from molybdic acid and zinc oxide and is hereby converted for the most part into liquid hydrocarbons of low boiling-point of gasoline character.

What we claim is:

1. In the process for destructively hydrogenating bituminous materials with hydrogen at atemperature and pressure'suitable for destructive hydrogenation and in which the hydrogen and bituminous material react with the evolution of heat and are passed at the pressure de-' sired for the destructive hydrogenation through a tortuous confined pathway heated to the destructive hydrogenation temperature, the method of avoiding localized superheating in said confined pathway which comprises heating said confined pathway by a mixture consisting of flame gases diluted with cool gases of c0mbustion to give said mixture atemperature at least 0. higher than the temperature of the de- 1 structive hydrogenation but below 800 C.

2. In the process for destructively hydrogenating bituminous materials with hydrogen at a pressure of about 200 atmospheres and at a temperature suitable for destructive hydrogenation and in which the hydrogen and bituminous material are passed at said pressure through a tortuous confined pathway in which they are heated to about 450 C., the method of avoiding localized superheatingin said confined pathway 

